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JP7341309B2 - Substrate processing method and substrate processing system - Google Patents
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JP7341309B2 - Substrate processing method and substrate processing system - Google Patents

Substrate processing method and substrate processing system Download PDF

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JP7341309B2
JP7341309B2 JP2022501788A JP2022501788A JP7341309B2 JP 7341309 B2 JP7341309 B2 JP 7341309B2 JP 2022501788 A JP2022501788 A JP 2022501788A JP 2022501788 A JP2022501788 A JP 2022501788A JP 7341309 B2 JP7341309 B2 JP 7341309B2
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organic component
oxide film
metal oxide
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祐介 齋藤
誠 村松
寛之 藤井
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Tokyo Electron Ltd
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Description

本開示は、基板処理方法及び基板処理システムに関する。 The present disclosure relates to a substrate processing method and a substrate processing system.

特許文献１に開示の、デバイス層をエッチングする方法は、基板上にデバイス層を堆積させることと、デバイス層上に、６ｎｍ未満の平均粒径を有するナノ結晶ダイヤモンド層を堆積させることと、ナノ結晶ダイヤモンド層からエッチマスクを形成することとを含む。さらに、上記方法は、エッチマスクを介してデバイス層をエッチングしてチャネルを形成することと、ナノ結晶ダイヤモンド層をアッシングすることを含む。特許文献１において、ナノ結晶ダイヤモンド層はＣＶＤプロセスを使用して堆積されている。 The method of etching a device layer disclosed in Patent Document 1 includes the steps of: depositing a device layer on a substrate; depositing a nanocrystalline diamond layer having an average grain size of less than 6 nm on the device layer; forming an etch mask from the crystalline diamond layer. Further, the method includes etching the device layer through an etch mask to form a channel and ashing the nanocrystalline diamond layer. In WO 2005/010000, a nanocrystalline diamond layer is deposited using a CVD process.

特開２０１７－２２４８２３号公報JP2017-224823A

本開示にかかる技術は、エッチング耐性が高く低コストで形成可能なマスクを用いてエッチングを行い、エッチング後に当該マスクを容易に除去可能な基板処理方法及び基板処理システムを提供する。 The technology according to the present disclosure provides a substrate processing method and a substrate processing system in which etching is performed using a mask that has high etching resistance and can be formed at low cost, and the mask can be easily removed after etching.

本開示の一態様は、基板を処理する基板処理方法であって、基板を処理する基板処理方法であって、有機金属錯体、溶媒及び添加物を含む塗布液を基板に塗布し、前記塗布液の液膜を形成する工程と、前記塗布液の液膜が形成された基板を加熱し、前記添加物に含まれる有機成分を含有する金属酸化膜である有機成分含有金属酸化膜を形成する工程と、前記有機成分含有金属酸化膜をマスクとしてドライエッチングを行う工程と、前記ドライエッチング後、前記有機成分含有金属酸化膜中の前記有機成分を除去する工程と、前記有機成分含有金属酸化膜から前記有機成分を除去した膜をウェットエッチングにより除去する工程と、を有する。 One aspect of the present disclosure is a substrate processing method for processing a substrate, the method comprising: applying a coating liquid containing an organometallic complex, a solvent, and an additive to a substrate; and a step of heating the substrate on which the liquid film of the coating liquid is formed to form an organic component-containing metal oxide film, which is a metal oxide film containing the organic component contained in the additive. a step of performing dry etching using the organic component-containing metal oxide film as a mask; a step of removing the organic component in the organic component-containing metal oxide film after the dry etching; and a step of removing the organic component from the organic component-containing metal oxide film. and a step of removing the film from which the organic component has been removed by wet etching.

本開示によれば、エッチング耐性が高く低コストで形成可能なマスクを用いてエッチングを行い、エッチング後に当該マスクを容易に除去可能な基板処理方法及び基板処理システムを提供することができる。 According to the present disclosure, it is possible to provide a substrate processing method and a substrate processing system in which etching is performed using a mask that has high etching resistance and can be formed at low cost, and the mask can be easily removed after etching.

本実施形態にかかる基板処理システムとしてのウェハ処理システムの構成の概略を模式的に示す図である。1 is a diagram schematically showing an outline of the configuration of a wafer processing system as a substrate processing system according to the present embodiment. 図１のウェハ処理システムで行われるウェハ処理の一例を説明するためのフローチャートである。2 is a flowchart for explaining an example of wafer processing performed in the wafer processing system of FIG. 1. FIG. ウェハ処理の各工程におけるウェハＷの状態を示す模式部分断面図である。FIG. 3 is a schematic partial cross-sectional view showing the state of the wafer W in each step of wafer processing. ウェハ処理中に形成される膜の構造を模式的に示す図である。FIG. 2 is a diagram schematically showing the structure of a film formed during wafer processing. 第１加熱装置及び第２加熱装置での加熱後のウェハＷにおける、チタン原子、酸素原子、炭素原子及びシリコン原子の質量密度の割合の深さ方向分布を示す図である。FIG. 3 is a diagram showing the depth distribution of the mass density ratios of titanium atoms, oxygen atoms, carbon atoms, and silicon atoms in the wafer W after heating in the first heating device and the second heating device. 紫外線照射処理がウェットエッチング処理に及ぼす影響を示す図である。FIG. 3 is a diagram showing the influence of ultraviolet irradiation treatment on wet etching treatment.

半導体デバイス等の製造工程では、半導体ウェハ（以下、「ウェハ」という。）に対して、フォトリソグラフィー処理が行われ、ウェハ上にレジストパターンが形成される。そして、このレジストパターンをマスクとして、処理対象層のエッチングが行われ、当該処理対象層に所望のパターンが形成される。 In the manufacturing process of semiconductor devices and the like, a photolithography process is performed on a semiconductor wafer (hereinafter referred to as a "wafer") to form a resist pattern on the wafer. Then, using this resist pattern as a mask, the layer to be processed is etched, and a desired pattern is formed in the layer to be processed.

ところで、半導体デバイスの微細化等に伴い、処理対象層のエッチングに際し、高アスペクト比でのエッチングが求められている。このための技術として、レジスト膜よりエッチング耐性の高いハードマスク層を、レジスト膜の下層に形成し、当該ハードマスク層をマスクとしてエッチングする技術が知られている。ハードマスク層としては、例えばＴＥＯＳ（Tetra Ethyl Orthosilicate）を原料として形成された酸化シリコン膜（以下、「ＴＥＯＳ膜」という。）が用いられる。しかし、３Ｄ ＮＡＮＤデバイスの出現等に伴い、よりエッチング耐性が高いハードマスク層が求められている。 Incidentally, with the miniaturization of semiconductor devices, etching with a high aspect ratio is required when etching a layer to be processed. As a technique for this purpose, a technique is known in which a hard mask layer having higher etching resistance than a resist film is formed under the resist film, and etching is performed using the hard mask layer as a mask. As the hard mask layer, for example, a silicon oxide film (hereinafter referred to as "TEOS film") formed using TEOS (Tetra Ethyl Orthosilicate) as a raw material is used. However, with the advent of 3D NAND devices, a hard mask layer with higher etching resistance is required.

特許文献１には、ＣＶＤプロセスを使用して堆積されたナノ結晶ダイヤモンド層をエッチマスクとして用いることが開示されている。しかし、ナノ結晶ダイヤモンド層はスループットが低いＣＶＤ法により形成されている。したがって、ナノ結晶ダイヤモンド層は、ＴＥＯＳ膜よりエッチング耐性が高いとしても、高コストである。ハードマスク層は、当該ハードマスク層をマスクとしたエッチング後に除去されるものであるため、そのようなものに高いコストをかけるのは好ましくない。
また、ハードマスク層は、当該ハードマスク層をマスクとしたエッチング後は、スループット等の観点から、容易に除去可能であることが求められる。US Pat. No. 5,001,202 discloses the use of a nanocrystalline diamond layer deposited using a CVD process as an etch mask. However, the nanocrystalline diamond layer is formed by a CVD method with low throughput. Therefore, even though nanocrystalline diamond layers are more etch resistant than TEOS films, they are more costly. Since the hard mask layer is removed after etching using the hard mask layer as a mask, it is not preferable to spend a high cost on such a layer.
Further, the hard mask layer is required to be easily removable after etching using the hard mask layer as a mask, from the viewpoint of throughput and the like.

そこで、本開示にかかる技術は、エッチング耐性が高く低コストで形成可能なマスクを用いてエッチングを行い、エッチング後に当該マスクを容易に除去可能な基板処理方法及び基板処理システムを提供する。エッチング耐性が高く低コストで形成可能なマスクであって当該マスクを用いたエッチング後に容易に除去可能なものを用いて、エッチングを行う、基板処理方法及び基板処理システムを提供する。なお、本明細書において、「マスクのエッチング耐性」とは、当該マスクを用いてドライエッチングしたときの当該マスクの耐性を意味する。 Therefore, the technology according to the present disclosure provides a substrate processing method and a substrate processing system in which etching is performed using a mask that has high etching resistance and can be formed at low cost, and the mask can be easily removed after etching. Provided are a substrate processing method and a substrate processing system in which etching is performed using a mask that has high etching resistance and can be formed at low cost and that can be easily removed after etching using the mask. Note that in this specification, "the etching resistance of a mask" means the resistance of the mask when dry etching is performed using the mask.

以下、本実施形態にかかる基板処理方法及び基板処理システムについて、図面を参照しながら説明する。なお、本明細書及び図面において、実質的に同一の機能構成を有する要素については、同一の符号を付することにより重複説明を省略する。 Hereinafter, a substrate processing method and a substrate processing system according to the present embodiment will be described with reference to the drawings. Note that, in this specification and the drawings, elements having substantially the same functional configurations are designated by the same reference numerals and redundant explanation will be omitted.

図１は、本実施形態にかかる基板処理システムとしてのウェハ処理システムの構成の概略を模式的に示す図である。 FIG. 1 is a diagram schematically showing the configuration of a wafer processing system as a substrate processing system according to this embodiment.

図示するように、ウェハ処理システムＫは、基板としてのウェハＷに所望の処理を行う３つの処理システム１～３を有している。また、ウェハ処理システムＫには、制御装置４が設けられている。制御装置４は、例えばＣＰＵやメモリ等を備えたコンピュータであり、プログラム格納部（図示せず）を有している。プログラム格納部には、ウェハ処理システムＫにおける各種処理を制御するプログラムが格納されている。なお、上記プログラムは、コンピュータに読み取り可能な非一時的な記憶媒体に記録されていたものであって、当該記憶媒体から制御装置４にインストールされたものであってもよい。プログラムの一部または全ては専用ハードウェア（回路基板）で実現してもよい。 As shown in the figure, the wafer processing system K includes three processing systems 1 to 3 that perform desired processing on a wafer W as a substrate. Further, the wafer processing system K is provided with a control device 4. The control device 4 is, for example, a computer equipped with a CPU, a memory, etc., and has a program storage section (not shown). The program storage unit stores programs for controlling various processes in the wafer processing system K. Note that the program may be one that has been recorded on a computer-readable non-temporary storage medium, and may have been installed in the control device 4 from the storage medium. Part or all of the program may be realized by dedicated hardware (circuit board).

第１処理システム１では、ウェハＷに対してフォトリソグラフィー処理等が行われる。第１処理システム１は、レジスト塗布装置１１と、現像装置１２と、液膜形成装置１３と、第１～第５加熱装置２１～２５と、を有する。 In the first processing system 1, photolithography processing and the like are performed on the wafer W. The first processing system 1 includes a resist coating device 11, a developing device 12, a liquid film forming device 13, and first to fifth heating devices 21 to 25.

レジスト塗布装置１１は、レジスト液をウェハＷに供給し、ウェハＷ上にレジスト液の液膜を形成する。
現像装置１２は、現像液を用いて、ウェハＷを現像処理する。The resist coating device 11 supplies a resist liquid to the wafer W and forms a liquid film of the resist liquid on the wafer W.
The developing device 12 develops the wafer W using a developer.

液膜形成装置１３は、有機金属錯体、溶媒及び添加物を含む塗布液としてのマスク層形成用液をウェハＷに塗布し、ウェハＷ上に当該マスク層形成用液の液膜を形成する。液膜形成装置１３は、レジスト塗布装置１１によるレジスト液膜の形成の前に、マスク層形成用液の液膜の形成を行う。マスク層用塗布液に含まれる有機金属錯体は、金属原子と炭素原子との結合を含む錯体であり、本実施形態では、有機チタン錯体であるものとする。溶媒には、例えば、プロピレングリコールメチルエーテル（ＰＧＭＥ）、プロピレングリコールモノメチルエーテルアセテート（ＰＧＭＥＡ）またはこれらを混合した溶媒を用いることができる。添加物には、濡れ性向上や乾燥抑制を目的とするものの他、後述の有機成分含有金属酸化膜の膜密度を向上させることを目的とした有機物（以下、「密度向上用有機物」という。）が含まれている。密度向上用有機物は、第１加熱装置２１及び第２加熱装置２２での加熱温度では分解せず膜内に残る有機化合物が用いられる。特に、第２加熱装置２２では、後述のように、有機チタン錯体の加水分解及び脱水縮合のため、高温で加熱が行われるが、密度向上用有機物は、このような第２加熱装置２２での高い加熱温度でも分解しない有機化合物が用いられる。 The liquid film forming device 13 applies a mask layer forming liquid as a coating liquid containing an organometallic complex, a solvent, and an additive to the wafer W, and forms a liquid film of the mask layer forming liquid on the wafer W. The liquid film forming device 13 forms a liquid film of a mask layer forming liquid before the resist coating device 11 forms a resist liquid film. The organometallic complex contained in the mask layer coating liquid is a complex containing a bond between a metal atom and a carbon atom, and in this embodiment, it is an organotitanium complex. As the solvent, for example, propylene glycol methyl ether (PGME), propylene glycol monomethyl ether acetate (PGMEA), or a mixture thereof can be used. Additives include those intended to improve wettability and suppress drying, as well as organic substances intended to improve the film density of the organic component-containing metal oxide film (hereinafter referred to as "density-enhancing organic substances"), which will be described later. It is included. As the density-improving organic substance, an organic compound that does not decompose at the heating temperatures of the first heating device 21 and the second heating device 22 and remains in the film is used. In particular, in the second heating device 22, heating is performed at a high temperature for hydrolysis and dehydration condensation of the organic titanium complex, as will be described later. An organic compound that does not decompose even at high heating temperatures is used.

レジスト塗布装置１１及び液膜形成装置１３は、スピン塗布法によりウェハＷに処理液を塗布し各種膜を形成するスピン塗布装置である。レジスト塗布装置１１及び液膜形成装置１３は、公知のスピン塗布装置と同様、ウェハＷが載置される載置台（図示せず）や、各種処理液を吐出する吐出ノズル（図示せず）、載置台を回転させることでウェハＷを回転させて処理液をウェハＷの表面に拡散させる回転機構（図示せず）等を有する。 The resist coating device 11 and the liquid film forming device 13 are spin coating devices that apply a processing liquid to the wafer W by a spin coating method to form various films. The resist coating device 11 and the liquid film forming device 13 are similar to known spin coating devices, and include a mounting table (not shown) on which the wafer W is mounted, a discharge nozzle (not shown) that discharges various processing liquids, It includes a rotation mechanism (not shown) that rotates the wafer W by rotating the mounting table and diffuses the processing liquid onto the surface of the wafer W.

第１加熱装置２１は、液膜形成装置１３によるマスク層形成用液の液膜形成後、ウェハＷを加熱する。第１加熱装置２１による加熱により、マスク層形成用液の液膜から溶媒等を除去する。
第２加熱装置２２は、第１加熱装置２１による加熱後、ウェハを加熱する。第２加熱装置２２による加熱により、後述の有機成分含有金属酸化膜としての有機成分含有酸化チタン膜が形成される。
第３加熱装置２３は、レジスト塗布装置１１によるレジスト液膜の形成後且つ露光装置（図示せず）による露光前に、ウェハＷを加熱する。つまり、第３加熱装置２３は、ＰＡＢ（Pre-applied bake）処理を行う。上述の露光装置は、例えば第１処理システム１に隣接する位置に設けられている。
第４加熱装置２４は、上記露光後且つ現像装置１２による現像前に、ウェハＷを加熱する。つまり、第４加熱装置２４は、ＰＥＢ（Post exposure bake）処理を行う。
第５加熱装置２５は、上記現像後、ウェハＷを加熱する。つまり、第５加熱装置２５はポストベイク処理を行う。The first heating device 21 heats the wafer W after the liquid film forming device 13 forms a liquid film of the mask layer forming liquid. By heating with the first heating device 21, the solvent and the like are removed from the liquid film of the mask layer forming liquid.
The second heating device 22 heats the wafer after being heated by the first heating device 21 . By heating with the second heating device 22, an organic component-containing titanium oxide film is formed as an organic component-containing metal oxide film to be described later.
The third heating device 23 heats the wafer W after the resist liquid film is formed by the resist coating device 11 and before exposure by the exposure device (not shown). That is, the third heating device 23 performs a PAB (Pre-applied bake) process. The above-mentioned exposure apparatus is provided, for example, at a position adjacent to the first processing system 1.
The fourth heating device 24 heats the wafer W after the exposure and before the development by the development device 12. That is, the fourth heating device 24 performs a PEB (Post exposure bake) process.
The fifth heating device 25 heats the wafer W after the development described above. That is, the fifth heating device 25 performs a post-bake process.

第１～第５加熱装置２１～２５は、公知の加熱装置と同様、ウェハＷが載置され当該ウェハＷを所定の温度で加熱する熱板（図示せず）等を有する。 Like known heating devices, the first to fifth heating devices 21 to 25 each have a hot plate (not shown) on which a wafer W is placed and heats the wafer W at a predetermined temperature.

その他、第１処理システム１には、装置間でウェハを搬送するためのウェハ搬送装置（図示せず）等が設けられている。 In addition, the first processing system 1 is provided with a wafer transport device (not shown) for transporting wafers between devices.

第２処理システム２では、ウェハＷに対してプラズマを用いたプラズマ処理、具体的には、プラズマを用いた、ウェハＷに対するドライエッチングが行われる。第２処理システム２は、第１ドライエッチング装置３１と、第２ドライエッチング装置３２とを有する。 In the second processing system 2, plasma processing using plasma is performed on the wafer W, specifically, dry etching is performed on the wafer W using plasma. The second processing system 2 includes a first dry etching device 31 and a second dry etching device 32.

第１ドライエッチング装置３１は、現像装置１２による現像によって形成されたレジストパターンをマスクとして、後述の有機成分含有酸化チタン膜をドライエッチングし、有機成分含有酸化チタン膜のパターンを形成する。
第２ドライエッチング装置３２は、上記有機成分含有酸化チタン膜のパターンをマスクとして、処理対象層をドライエッチングする。処理対象層は例えば有機成分含有酸化チタン膜の直下に形成されている、アモルファスシリコン層や、タングステン（Ｗ）を含むＷＢＣ層等の金属炭化層である。
第１ドライエッチング装置３１及び第２ドライエッチング装置３２には、公知のエッチング装置を用いることができ、例えばＲＩＥ（Reactive Ion Etching）装置が用いられる。The first dry etching device 31 uses the resist pattern formed by development by the developing device 12 as a mask to dry-etch the organic component-containing titanium oxide film, which will be described later, to form a pattern of the organic component-containing titanium oxide film.
The second dry etching device 32 dry-etches the target layer using the pattern of the organic component-containing titanium oxide film as a mask. The layer to be processed is, for example, a metal carbide layer such as an amorphous silicon layer or a WBC layer containing tungsten (W), which is formed directly under the organic component-containing titanium oxide film.
A known etching device can be used as the first dry etching device 31 and the second dry etching device 32, such as an RIE (Reactive Ion Etching) device.

その他、第２処理システム２には、装置間でウェハを搬送するためのウェハ搬送装置（図示せず）等が設けられている。 In addition, the second processing system 2 is provided with a wafer transport device (not shown) for transporting wafers between devices.

第３処理システム３では、ウェハＷに対して、有機成分含有金属酸化膜のパターンの除去処理等が行われる。第３処理システム３は、除去装置４１と、ウェットエッチング装置４２とを有する。 In the third processing system 3, the wafer W is subjected to a process such as removing a pattern of a metal oxide film containing an organic component. The third processing system 3 includes a removal device 41 and a wet etching device 42.

除去装置４１は、第２ドライエッチング装置３２によるドライエッチング後、有機成分含有酸化チタン膜中の有機成分を除去する。具体的には、除去装置４１は、上記ドライエッチング後、有機成分含有酸化チタン膜のパターン中の、密度向上用有機物を除去する。例えば、除去装置４１は、エネルギー線としての紫外線をウェハＷに照射しながら当該ウェハＷを加熱することで、密度向上用有機物を除去し、有機成分含有酸化チタン膜のパターンを酸化チタン膜とする。この場合、除去装置４１は、例えば、ウェハＷが載置される載置台（図示せず）や、ピーク波長が１７２ｎｍの紫外線を載置台上のウェハＷに照射するキセノンフラッシュランプ又は重水素ランプ等のＵＶ光源（図示せず）、載置台に埋設された抵抗加熱ヒータ等の加熱機構（図示せず）を有する。なお、除去装置４１が、載置台が内部に配設される処理容器（図示せず）をさらに有し、ＵＶ光源が処理容器の外部に設けられ当該処理容器に設けられた光学窓を介して紫外線をウェハＷに照射するようにしてもよい。上述のＵＶ光源は、ウェハＷの全面に対して紫外線を照射可能に構成される。なお、照射する紫外線のピーク波長は、１７２ｎｍに限定されず、例えば１５０ｎｍ～２００ｎｍであればよい。 The removal device 41 removes the organic component in the organic component-containing titanium oxide film after dry etching by the second dry etching device 32. Specifically, the removal device 41 removes the density-enhancing organic substance in the pattern of the organic component-containing titanium oxide film after the dry etching. For example, the removal device 41 heats the wafer W while irradiating the wafer W with ultraviolet rays as energy rays, thereby removing the density-enhancing organic substance and changing the pattern of the organic component-containing titanium oxide film to a titanium oxide film. . In this case, the removal device 41 may include, for example, a mounting table (not shown) on which the wafer W is mounted, a xenon flash lamp or a deuterium lamp that irradiates the wafer W on the mounting table with ultraviolet light having a peak wavelength of 172 nm, or the like. It has a UV light source (not shown) and a heating mechanism (not shown) such as a resistance heater embedded in the mounting table. Note that the removal device 41 further includes a processing container (not shown) in which a mounting table is disposed, and a UV light source is provided outside the processing container and illuminates through an optical window provided in the processing container. The wafer W may be irradiated with ultraviolet light. The UV light source described above is configured to be able to irradiate the entire surface of the wafer W with ultraviolet rays. Note that the peak wavelength of the ultraviolet rays to be irradiated is not limited to 172 nm, and may be, for example, 150 nm to 200 nm.

ウェットエッチング装置４２は、有機成分含有酸化チタン膜のパターンから有機成分すなわち密度向上用有機物を除去した膜を、ウェットエッチングにより除去する。
ウェットエッチング装置４２には、公知の装置を用いることができる。The wet etching device 42 removes the organic component, that is, the density-enhancing organic substance removed from the pattern of the organic component-containing titanium oxide film by wet etching.
A known device can be used as the wet etching device 42.

その他、第３処理システム３には、装置間でウェハＷを搬送するためのウェハ搬送装置（図示せず）等が設けられている。 In addition, the third processing system 3 is provided with a wafer transport device (not shown) for transporting the wafer W between devices.

続いて、以上のように構成されたウェハ処理システムＫで行われるウェハ処理の一例について説明する。図２は、ウェハ処理の一例を説明するためのフローチャートである。図３は、ウェハ処理の各工程におけるウェハＷの状態を示す模式部分断面図である。図４は、ウェハ処理中に形成される膜の構造を模式的に示す図である。なお、ウェハ処理が行われるウェハＷの表面には、図３（Ａ）に示すように、処理対象層としてのアモルファスシリコン膜（以下、「ａ－Ｓｉ膜」という。）Ｆ１が予め形成されている。 Next, an example of wafer processing performed in the wafer processing system K configured as above will be described. FIG. 2 is a flowchart for explaining an example of wafer processing. FIG. 3 is a schematic partial cross-sectional view showing the state of the wafer W in each step of wafer processing. FIG. 4 is a diagram schematically showing the structure of a film formed during wafer processing. Note that, as shown in FIG. 3A, an amorphous silicon film (hereinafter referred to as "a-Si film") F1 as a layer to be processed is formed in advance on the surface of the wafer W on which wafer processing is performed. There is.

（マスク層形成用液の液膜形成）
まず、図２及び図３（Ａ）に示すように、第１処理システム１の液膜形成装置１３において、有機チタン錯体等を含むマスク層形成用液がウェハＷの表面に回転塗布され、ａ－Ｓｉ膜Ｆ１を覆うようにマスク層形成用液の液膜Ｆ２が形成される（ステップＳ１）。図４（Ａ）に示すように、マスク層形成用液の液膜Ｆ２の状態では、チタン原子Ｍとリガンド（Ｒ）Ｌとを含む有機チタン錯体Ｃは互いに独立しており、チタン原子Ｍ同士は結合していない。また、マスク層形成用液の液膜Ｆ２には、添加物Ａが含有されている。なお、図示は省略するが、マスク層形成用液の液膜Ｆ２中には溶媒も含有されている。(Liquid film formation of mask layer forming liquid)
First, as shown in FIGS. 2 and 3A, in the liquid film forming apparatus 13 of the first processing system 1, a mask layer forming liquid containing an organic titanium complex or the like is spin-coated onto the surface of the wafer W, and a - A liquid film F2 of mask layer forming liquid is formed to cover the Si film F1 (step S1). As shown in FIG. 4(A), in the state of the liquid film F2 of the mask layer forming liquid, the organic titanium complexes C containing titanium atoms M and ligands (R)L are independent of each other, and the titanium atoms M are are not combined. Moreover, the additive A is contained in the liquid film F2 of the mask layer forming liquid. Although not shown, the liquid film F2 of the mask layer forming liquid also contains a solvent.

（有機成分含有酸化チタン膜の形成）
次いで、マスク層形成用液の液膜Ｆ２が形成されたウェハＷが加熱され、図３（Ｂ）に示すように、有機成分含有金属酸化膜としての有機成分含有酸化チタン膜Ｆ３が形成され、具体的には、ａ－Ｓｉ膜Ｆ１上の液膜Ｆ２が、有機成分含有酸化チタン膜Ｆ３となる（ステップＳ２）。有機成分含有金属酸化膜とは、マスク形成用液の添加物に含まれていた密度向上用有機物を含有する金属酸化膜であり、具体的には、密度向上用有機物が金属酸化膜構造の中に入り込んだような形態で存在する膜である。(Formation of organic component-containing titanium oxide film)
Next, the wafer W on which the liquid film F2 of the mask layer forming liquid has been formed is heated, and as shown in FIG. 3(B), an organic component-containing titanium oxide film F3 as an organic component-containing metal oxide film is formed. Specifically, the liquid film F2 on the a-Si film F1 becomes an organic component-containing titanium oxide film F3 (step S2). A metal oxide film containing an organic component is a metal oxide film that contains a density-enhancing organic substance that was included in the additives of the mask forming liquid. Specifically, the density-enhancing organic substance is contained in the metal oxide film structure. It is a membrane that exists in a form that looks like it has entered the inside of the body.

ステップＳ２の工程では、より具体的には、まず、第１加熱装置２１において、マスク層形成用液の液膜Ｆ２が形成されたウェハＷが第１温度Ｔ１で加熱され、当該液膜Ｆ２内の溶媒が除去される。このとき、不要な添加物、具体的には密度向上用有機物以外の添加物も除去される。第１温度Ｔ１は、マスク層形成用液中の溶媒の沸点より高く後述の加水分解及び脱水縮合が生じない温度、例えば１５０℃～３００℃である。 More specifically, in the process of step S2, first, in the first heating device 21, the wafer W on which the liquid film F2 of the mask layer forming liquid is formed is heated at a first temperature T1, and the inside of the liquid film F2 is heated. of solvent is removed. At this time, unnecessary additives, specifically additives other than the density-improving organic substance, are also removed. The first temperature T1 is a temperature higher than the boiling point of the solvent in the mask layer forming liquid at which hydrolysis and dehydration condensation described below do not occur, for example, 150°C to 300°C.

続いて、第２加熱装置２２において、溶媒等が除去されたウェハＷが、例えば大気ガス雰囲気下で、第１温度Ｔ１より高い第２温度Ｔ２で加熱される。この加熱の結果、大気中の水分と酸素により、図４（Ｂ）に示すように有機チタン錯体Ｃが加水分解されると共に、加水分解された有機チタン錯体Ｃが脱水縮合され、図４（Ｃ）に示すように、チタン原子Ｍ同士が酸素（Ｏ）を介して結合され、酸化チタン膜構造ＭＳが形成される。加水分解及び脱水縮合の過程において、密度向上用有機物Ｙは、除去されず、酸化チタン膜構造ＭＳの中に入り込んだような形態で膜中に残る。有機成分含有酸化チタン膜Ｆ３は、このように、密度向上用有機物Ｙが酸化チタン膜構造ＭＳの中に入り込んだような形態で存在する膜である。
なお、第２加熱装置２２での加熱後の有機成分含有酸化チタン膜Ｆ３の厚さは、例えば２０～５００ｎｍである。また、上述の第２温度Ｔ２は例えば３５０～６００℃である。Subsequently, in the second heating device 22, the wafer W from which the solvent and the like have been removed is heated at a second temperature T2 higher than the first temperature T1, for example, in an atmospheric gas atmosphere. As a result of this heating, the organic titanium complex C is hydrolyzed by moisture and oxygen in the atmosphere as shown in FIG. 4(B), and the hydrolyzed organic titanium complex C is dehydrated and condensed. ), titanium atoms M are bonded to each other via oxygen (O) to form a titanium oxide film structure MS. In the process of hydrolysis and dehydration condensation, the density-enhancing organic substance Y is not removed and remains in the film in a form that appears to have entered the titanium oxide film structure MS. The organic component-containing titanium oxide film F3 is thus a film in which the density-enhancing organic substance Y has entered the titanium oxide film structure MS.
Note that the thickness of the organic component-containing titanium oxide film F3 after heating with the second heating device 22 is, for example, 20 to 500 nm. Further, the second temperature T2 mentioned above is, for example, 350 to 600°C.

有機成分含有酸化チタン膜Ｆ３に含まれる密度向上用有機物Ｙは、前述のように、第１加熱装置２１及び第２加熱装置２２での加熱温度では分解しない有機化合物である。具体的には、密度向上用有機物Ｙは、例えば、容易に分解することがない高分子の有機物である。ただし、炭素原子間が単結合のみである鎖式化合物である場合、分子量が高すぎると、金属酸化膜構造が正常に形成されない場合がある。その場合は、密度向上用有機物Ｙとして、分子量が比較的小さくても容易に分解することがない、環式有機化合物や炭素原子間に不飽和結合を含む鎖式化合物等が用いられる。 The density-enhancing organic substance Y contained in the organic component-containing titanium oxide film F3 is an organic compound that does not decompose at the heating temperatures in the first heating device 21 and the second heating device 22, as described above. Specifically, the density-enhancing organic substance Y is, for example, a polymeric organic substance that does not easily decompose. However, in the case of a chain compound having only a single bond between carbon atoms, if the molecular weight is too high, a metal oxide film structure may not be formed normally. In that case, as the density-enhancing organic substance Y, a cyclic organic compound or a chain compound containing an unsaturated bond between carbon atoms, etc., which are not easily decomposed even if the molecular weight is relatively small, are used.

図５は、第１加熱装置２１及び第２加熱装置２２での加熱後のウェハＷにおける、チタン原子、酸素原子、炭素原子及びシリコン原子の原子組成百分率（ａｔｏｍ％）の深さ方向分布を示す図である。図には、ベアシリコンウェハ上に厚さが約４００ｎｍの有機成分含有酸化チタン膜Ｆ３を形成したときの例が示されている。
図示するように、第１加熱装置２１及び第２加熱装置２２で加熱された後の有機成分含有酸化チタン膜Ｆ３において、チタン原子、酸素原子及び炭素原子の原子組成百分率は深さ方向に偏りがなく、略一様であり、言い換えると、組成比が深さ方向に関して略一様である。また、第１加熱装置２１及び第２加熱装置２２で加熱された後の有機成分含有酸化チタン膜Ｆ３中の炭素原子の割合は約５０％であり比較的高い。
これらのことから、第１加熱装置２１及び第２加熱装置２２での加熱後の膜には、マスク層形成用液に含まれる有機成分が除去されずに残っていることが分かる。
なお、原子組成百分率からみると、有機成分含有酸化チタン膜Ｆ３は一酸化チタンの構造に近いと思われる。しかし、有機成分含有酸化チタン膜Ｆ３の構造は、加熱により反応が進み形成されたチタン原子と酸素原子との結合（Ｔｉ－Ｏ結合）の部分と、未反応のチタン原子とリガンドとの結合（Ｔｉ－Ｒ結合）の部分とが混在しており、その全体が純粋な一酸化チタンの構造、二酸化チタンの構造等を成すものではない、と推測される。
また、本発明者らは、第２加熱装置２２での加熱温度がある温度（例えば６００℃）以上になると、有機成分含有酸化チタン膜Ｆ３の膜厚が下がることを確認している。これは、第２加熱装置２２での加熱温度がある温度以上になると、密度向上用有機物が分解し始めるから、と考えられる。FIG. 5 shows the depth distribution of the atomic composition percentages (atom%) of titanium atoms, oxygen atoms, carbon atoms, and silicon atoms in the wafer W after heating in the first heating device 21 and the second heating device 22. It is a diagram. The figure shows an example in which an organic component-containing titanium oxide film F3 having a thickness of about 400 nm is formed on a bare silicon wafer.
As shown in the figure, in the organic component-containing titanium oxide film F3 after being heated by the first heating device 21 and the second heating device 22, the atomic composition percentages of titanium atoms, oxygen atoms, and carbon atoms are uneven in the depth direction. In other words, the composition ratio is substantially uniform in the depth direction. Further, the proportion of carbon atoms in the organic component-containing titanium oxide film F3 after being heated by the first heating device 21 and the second heating device 22 is about 50%, which is relatively high.
From these facts, it can be seen that the organic components contained in the mask layer forming liquid remain in the film after being heated by the first heating device 21 and the second heating device 22 without being removed.
Note that, in terms of atomic composition percentage, it seems that the organic component-containing titanium oxide film F3 has a structure close to that of titanium monoxide. However, the structure of the organic component-containing titanium oxide film F3 consists of a bond between a titanium atom and an oxygen atom (Ti-O bond) formed by a reaction caused by heating, and a bond between an unreacted titanium atom and a ligand ( It is presumed that the entire structure does not form a pure titanium monoxide structure, a titanium dioxide structure, etc.
Further, the present inventors have confirmed that when the heating temperature in the second heating device 22 exceeds a certain temperature (for example, 600° C.), the thickness of the organic component-containing titanium oxide film F3 decreases. This is thought to be because when the heating temperature in the second heating device 22 reaches a certain temperature or higher, the density-enhancing organic substance begins to decompose.

ウェハ処理の説明に戻る。 Returning to the explanation of wafer processing.

（レジストパターンの形成）
有機成分含有酸化チタン膜Ｆ３の形成後、レジストパターンが形成される（ステップＳ３）。
具体的には、まず、レジスト塗布装置１１において、ウェハＷの表面にレジスト液が回転塗布され、有機成分含有酸化チタン膜Ｆ３を覆うように、レジスト液の液膜が形成される。
続いて、第３加熱装置２３において、ウェハＷがＰＡＢ処理され、図３（Ｃ）に示すように、有機成分含有酸化チタン膜Ｆ３上にレジスト膜Ｆ４が形成される。
次に、露光装置（図示せず）において、ウェハが所望のパターンで露光処理される。
次いで、第４加熱装置２４において、ウェハＷがＰＥＢ処理される。
そして、現像装置１２において、ウェハＷが現像処理され、図３（Ｄ）に示すように、レジストパターンＦ５が形成される。その後、第５加熱装置２５において、ウェハＷがボスとベーク処理される。(Formation of resist pattern)
After forming the organic component-containing titanium oxide film F3, a resist pattern is formed (step S3).
Specifically, first, in the resist coating device 11, a resist solution is spin-coated onto the surface of the wafer W, and a liquid film of the resist solution is formed so as to cover the organic component-containing titanium oxide film F3.
Subsequently, in the third heating device 23, the wafer W is subjected to PAB processing, and as shown in FIG. 3(C), a resist film F4 is formed on the organic component-containing titanium oxide film F3.
Next, in an exposure apparatus (not shown), the wafer is subjected to exposure processing in a desired pattern.
Next, in the fourth heating device 24, the wafer W is subjected to PEB processing.
Then, in the developing device 12, the wafer W is developed, and a resist pattern F5 is formed as shown in FIG. 3(D). Thereafter, in the fifth heating device 25, the wafer W is baked with the boss.

（レジストパターンの転写）
レジストパターンＦ５の形成後、当該レジストパターンＦ５が有機成分含有酸化チタン膜Ｆ３に転写され、図３（Ｅ）に示すように、有機成分含有酸化チタン膜のパターンＦ６が形成される（ステップＳ４）。
具体的には、例えば、ウェハＷが、第２処理システム２に搬入され、第１ドライエッチング装置３１において、レジストパターンＦ５をマスクとして、有機成分含有酸化チタン膜Ｆ３がドライエッチングされ、レジストパターンＦ５が有するパターンが有機成分含有酸化チタン膜Ｆ３に転写される。そして、アッシング装置（図示せず）において、レジストパターンＦ５が除去され、図３（Ｅ）に示すように、有機成分含有酸化チタン膜のパターンＦ６が形成される。有機成分含有酸化チタン膜Ｆ３のドライエッチングには、例えば塩素（Ｃｌ２）ガスや三塩化ホウ素（ＢＣｌ３）ガスが用いられる。(Transfer of resist pattern)
After forming the resist pattern F5, the resist pattern F5 is transferred to the organic component-containing titanium oxide film F3, and as shown in FIG. 3(E), a pattern F6 of the organic component-containing titanium oxide film is formed (step S4). .
Specifically, for example, the wafer W is carried into the second processing system 2, and the organic component-containing titanium oxide film F3 is dry-etched in the first dry etching device 31 using the resist pattern F5 as a mask to form the resist pattern F5. The pattern is transferred to the organic component-containing titanium oxide film F3. Then, in an ashing device (not shown), the resist pattern F5 is removed, and a pattern F6 of a titanium oxide film containing an organic component is formed as shown in FIG. 3(E). For example, chlorine (Cl 2 ) gas or boron trichloride (BCl 3 ) gas is used for dry etching the organic component-containing titanium oxide film F3.

（処理対象層のドライエッチング）
次いで、第２ドライエッチング装置３２において、有機成分含有酸化チタン膜のパターンＦ６をマスクとして、処理対象層であるａ－Ｓｉ膜Ｆ１がドライエッチングされる（ステップＳ５）。処理対象層のドライエッチングには、Ｃｌ系ガスが用いられる。Ｃｌ系ガスとは、Ｃｌ（塩素）を含むガスであり、例えば、塩化水素（ＨＣｌ）ガス等である。また、Ｃｌ系ガスに代えて、フッ素（Ｆ）を含む六フッ化硫黄（ＳＦ６）ガス等のＦ系ガスを用いてもよい。(Dry etching of the layer to be treated)
Next, in the second dry etching device 32, the a-Si film F1, which is the layer to be processed, is dry etched using the pattern F6 of the organic component-containing titanium oxide film as a mask (step S5). A Cl-based gas is used for dry etching of the layer to be processed. The Cl-based gas is a gas containing Cl (chlorine), such as hydrogen chloride (HCl) gas. Further, instead of the Cl-based gas, an F-based gas such as sulfur hexafluoride (SF 6 ) gas containing fluorine (F) may be used.

（有機成分の除去）
その後、有機成分含有酸化チタン膜のパターンＦ６から密度向上用有機物Ｙが除去される（ステップＳ６）。これにより、有機成分含有酸化チタン膜のパターンＦ６は、図３（Ｆ）に示すように、密度向上用有機物Ｙを含まない酸化チタン膜のパターンＦ７となる。
ステップＳ６では、具体的には、ウェハＷが、第３処理システム３に搬入され、除去装置４１において、ウェハＷが第３温度Ｔ３で加熱され、その状態で、当該ウェハＷに紫外線が照射され、密度向上用有機物Ｙが除去される。紫外線の照射は、例えば大気ガス雰囲気下で行われる。大気ガス雰囲気下での紫外線照射により生じたオゾンや活性酸素によって密度向上用有機物Ｙが酸化される。酸化した密度向上用有機物Ｙは揮発され除去されるところ、加熱することで揮発速度を高めることができる。なお、第３温度Ｔ３を高くするほど、密度向上用有機物Ｙの除去を高速で行うことができる。第３温度Ｔ３は例えば２００～６００℃である。(Removal of organic components)
Thereafter, the density-enhancing organic substance Y is removed from the pattern F6 of the organic component-containing titanium oxide film (step S6). As a result, the pattern F6 of the titanium oxide film containing an organic component becomes a pattern F7 of a titanium oxide film that does not contain the density-enhancing organic substance Y, as shown in FIG. 3(F).
In step S6, specifically, the wafer W is carried into the third processing system 3, the wafer W is heated at the third temperature T3 in the removal device 41, and in that state, the wafer W is irradiated with ultraviolet rays. , the density-enhancing organic substance Y is removed. Irradiation with ultraviolet light is performed, for example, under an atmospheric gas atmosphere. The density-enhancing organic substance Y is oxidized by ozone and active oxygen generated by ultraviolet irradiation in an atmospheric gas atmosphere. The oxidized density-enhancing organic substance Y is volatilized and removed, and the rate of volatilization can be increased by heating. Note that the higher the third temperature T3 is, the faster the density-enhancing organic substance Y can be removed. The third temperature T3 is, for example, 200 to 600°C.

（ウェットエッチング）
そして、ウェットエッチング装置４２において、密度向上用有機物Ｙを含まない酸化チタン膜のパターンＦ７がウェットエッチングにより除去される（ステップＳ７）。エッチング液には、例えば希フッ酸を用いることができる。希フッ酸の代わりに、ＳＰＭ（Sulfuric acid Peroxide Mixture：硫酸過水）を用いてもよい。
酸化チタン膜のパターンＦ７が厚い場合等においては、ステップＳ６の有機成分の除去処理とステップＳ７のウェットエッチング処理とを交互に繰り返すようにしてもよい。(wet etching)
Then, in the wet etching device 42, the pattern F7 of the titanium oxide film that does not contain the density-enhancing organic substance Y is removed by wet etching (step S7). For example, dilute hydrofluoric acid can be used as the etching solution. SPM (Sulfuric acid peroxide mixture) may be used instead of dilute hydrofluoric acid.
When the pattern F7 of the titanium oxide film is thick, the organic component removal process in step S6 and the wet etching process in step S7 may be repeated alternately.

以上で、ウェハ処理システムＫで行われるウェハ処理が完了する。 With this, the wafer processing performed by the wafer processing system K is completed.

図６は、紫外線照射処理がウェットエッチング処理に及ぼす影響を示す図である。図には、ベアシリコンウェハ上に全面に亘って形成された有機成分含有酸化チタン膜に、紫外線照射処理を行った後に、０．５％希フッ酸でウェットエッチングを行った場合と、紫外線照射処理を行わずに同ウェットエッチングを場合の結果が示されている。０．５％希フッ酸は、ＣＶＤ法等により形成された酸化チタン膜のウェットエッチングに用いられるものである。図において、横軸は処理時間を示し、縦軸はウェットエッチング後の残膜厚を示している。なお、紫外線照射処理では、ピーク波長が１７２ｎｍの紫外線を照射した。 FIG. 6 is a diagram showing the influence of ultraviolet irradiation treatment on wet etching treatment. The figure shows a case in which a titanium oxide film containing an organic component formed over the entire surface of a bare silicon wafer was subjected to ultraviolet irradiation treatment and then wet etched with 0.5% diluted hydrofluoric acid. The results are shown when the same wet etching is performed without any treatment. 0.5% dilute hydrofluoric acid is used for wet etching of a titanium oxide film formed by CVD method or the like. In the figure, the horizontal axis shows the processing time, and the vertical axis shows the remaining film thickness after wet etching. In addition, in the ultraviolet irradiation treatment, ultraviolet rays having a peak wavelength of 172 nm were irradiated.

図に示すように、紫外線照射処理を行わない場合、ウェットエッチングの処理時間が３００秒では３０ｎｍ程度しか減少しない。それに対し、紫外線照射処理を行った場合、ウェットエッチングの処理時間が同じ３００秒でも、有機成分含有酸化チタン膜の厚さは２５０ｎｍ程度と、紫外線照射処理を行わなかった場合より、約８倍減少する。
このことから、有機成分含有酸化チタン膜は、紫外線照射処理を行うことで、短時間で容易に剥離することができることが分かる。なお、紫外線照射処理により、有機成分含有酸化チタン膜のウェットエッチングの速度が高くなる理由としては、密度向上用有機物によって希フッ酸と酸化チタン構造との反応が阻害されるのに対し、紫外線照射処理により密度向上用有機物が減少し上記反応が阻害されなくなったことが考えられる。As shown in the figure, when no ultraviolet irradiation treatment is performed and the wet etching treatment time is 300 seconds, the reduction is only about 30 nm. On the other hand, when ultraviolet irradiation treatment is performed, the thickness of the organic component-containing titanium oxide film is approximately 250 nm, which is approximately 8 times less than when no ultraviolet irradiation treatment is performed, even if the wet etching time is the same, 300 seconds. do.
This shows that the organic component-containing titanium oxide film can be easily peeled off in a short time by performing ultraviolet irradiation treatment. The reason why the rate of wet etching of titanium oxide films containing organic components increases with ultraviolet irradiation treatment is that the reaction between dilute hydrofluoric acid and the titanium oxide structure is inhibited by the density-enhancing organic substance, whereas ultraviolet irradiation It is considered that the density-enhancing organic substances were reduced by the treatment and the above reaction was no longer inhibited.

図に示した結果では、紫外線照射処理した場合において、ウェットエッチングの処理時間が３００秒を超えると、ウェットエッチングの処理時間によらず残膜厚はほとんど変わらず、ウェットエッチングの処理時間が９００秒でも有機成分含有酸化チタン膜は８０ｎｍ程度残っている。ただし、有機成分含有酸化チタン膜を薄くしたり、紫外線照射量を調整したり、紫外線の波長を変更することで、有機成分含有酸化チタン膜はウェットエッチングにより除去可能である。 The results shown in the figure show that in the case of ultraviolet irradiation treatment, when the wet etching time exceeds 300 seconds, the remaining film thickness remains almost unchanged regardless of the wet etching time; However, about 80 nm of the organic component-containing titanium oxide film remains. However, the organic component-containing titanium oxide film can be removed by wet etching by thinning the organic component-containing titanium oxide film, adjusting the amount of ultraviolet irradiation, or changing the wavelength of the ultraviolet rays.

以上のように、本実施形態にかかる基板処理方法は、有機金属錯体、溶媒及び添加物を含むマスク層形成用液をウェハＷに塗布し、マスク層形成用液の液膜を形成する工程と、上記液膜が形成されたウェハＷを加熱し、添加物に含まれる有機成分を含有する金属酸化膜である有機成分含有金属酸化膜を形成する工程と、有機成分含有金属酸化膜をマスクとしてドライエッチングを行う工程と、を有する。つまり、本実施形態では、処理対象層のドライエッチングを行う際に有機成分含有金属酸化膜をマスクとしている。有機成分含有金属酸化膜は、マスク層形成用液の塗布と加熱のみで形成可能であり、高スループットで形成可能であるため、低コストである。また、有機成分含有金属酸化膜は、ＴＥＯＳ膜のシリコン原子が金属原子に置き換わったような金属酸化膜を骨格としており、且つ、シリコン原子に比べて金属原子は揮発しにくいため、ＴＥＯＳ膜よりエッチング耐性が高い。さらに、有機成分含有金属酸化膜は、有機成分を含有しているため密度が高いので、さらに高いエッチング耐性を有する。実際に、本発明者らが行った試験によれば、Ｃｌ系ガスを用いたａ－Ｓｉ膜Ｆ１をドライエッチングするときの、有機成分含有金属酸化膜の一例である有機成分含有酸化チタン膜の選択比は、ドライエッチング時のウェハＷの温度が４００℃のときに、ＴＥＯＳ膜の４．９倍であり、同様に、５００℃のときに５．９倍、６００℃のときに５．７倍であった。したがって、本実施形態によれば、エッチング耐性が高いマスクを用いてドライエッチングを行う基板処理方法を提供することができる。
また、本実施形態にかかる基板処理方法は、有機成分含有金属酸化膜をマスクとしたドライエッチング後、当該有機成分含有金属酸化膜中の有機成分を除去する工程と、有機成分含有金属酸化膜から有機成分を除去した膜をウェットエッチングにより除去する工程と、を有する。この二つの工程で、マスクとして用いられた、高エッチング耐性の有機成分含有金属酸化膜を容易に除去することができる。
よって、本実施形態によれば、エッチング耐性が高く低コストで形成可能なマスクを用いてエッチングを行い、エッチング後に当該マスクを容易に除去可能な基板処理方法を提供することができる。As described above, the substrate processing method according to the present embodiment includes the steps of applying a mask layer forming liquid containing an organometallic complex, a solvent, and an additive to the wafer W to form a liquid film of the mask layer forming liquid. , a step of heating the wafer W on which the liquid film is formed to form an organic component-containing metal oxide film, which is a metal oxide film containing an organic component contained in the additive, and using the organic component-containing metal oxide film as a mask. and a step of performing dry etching. That is, in this embodiment, the organic component-containing metal oxide film is used as a mask when performing dry etching of the layer to be processed. The organic component-containing metal oxide film can be formed only by applying a mask layer forming liquid and heating, and can be formed with high throughput, so it is low cost. In addition, metal oxide films containing organic components have a metal oxide film skeleton in which the silicon atoms in the TEOS film are replaced with metal atoms, and metal atoms are less likely to volatilize than silicon atoms, so they are easier to etch than the TEOS film. Highly resistant. Furthermore, since the organic component-containing metal oxide film contains an organic component and has a high density, it has even higher etching resistance. In fact, according to tests conducted by the present inventors, when dry etching the a-Si film F1 using Cl-based gas, the organic component-containing titanium oxide film, which is an example of an organic component-containing metal oxide film, was The selectivity is 4.9 times that of the TEOS film when the temperature of the wafer W during dry etching is 400°C, similarly, it is 5.9 times that of the TEOS film when the temperature of the wafer W during dry etching is 500°C, and it is 5.7 times when the temperature of the wafer W is 600°C. It was double that. Therefore, according to this embodiment, it is possible to provide a substrate processing method in which dry etching is performed using a mask with high etching resistance.
Further, the substrate processing method according to the present embodiment includes a step of removing an organic component in the organic component-containing metal oxide film after dry etching using the organic component-containing metal oxide film as a mask, and removing the organic component from the organic component-containing metal oxide film. and a step of removing the film from which organic components have been removed by wet etching. With these two steps, the highly etching resistant organic component-containing metal oxide film used as a mask can be easily removed.
Therefore, according to the present embodiment, it is possible to provide a substrate processing method in which etching is performed using a mask that has high etching resistance and can be formed at low cost, and the mask can be easily removed after etching.

本実施形態では、上述のようにマスク用の金属酸化膜中にあえて有機物を残している。このように有機物を残すと、当該金属酸化膜が不要になったときに除去が困難である。そこで、エッチング後に金属酸化膜中から上述の有機物を除去するようにしている。 In this embodiment, as described above, organic substances are intentionally left in the metal oxide film for the mask. If organic substances remain in this way, it is difficult to remove the metal oxide film when it is no longer needed. Therefore, the above-mentioned organic substances are removed from the metal oxide film after etching.

また、本実施形態では、有機成分含有金属酸化膜のパターンを除去するためのウェットエッチングの処理時間が短くても、当該パターンを除去することができる。したがって、有機成分含有金属酸化膜のパターンより下層の構造物が上記ウェットエッチングによって受けるダメージを低減することができる。 Further, in this embodiment, even if the wet etching process time for removing the pattern of the organic component-containing metal oxide film is short, the pattern can be removed. Therefore, it is possible to reduce damage caused to the structure below the pattern of the organic component-containing metal oxide film by the wet etching.

さらに、有機成分含有金属酸化膜は、エッチング耐性が高いため、薄く形成してもよい。薄く形成すれば、有機成分含有金属酸化膜へのレジストパターンの転写をより正確に行うことができ、また、有機成分含有金属酸化膜の除去をより容易に行うことができる。 Furthermore, since the organic component-containing metal oxide film has high etching resistance, it may be formed thin. If the resist pattern is formed thinly, the resist pattern can be more accurately transferred to the organic component-containing metal oxide film, and the organic component-containing metal oxide film can be more easily removed.

以上の説明では、密度向上用有機物の除去処理は、紫外線照射しながら加熱する処理であった。紫外線の代わりに、電子線等の他のエネルギー線を照射してもよい。また、密度向上用有機物の除去処理は、エネルギー線は照射せずに単純にウェハＷを高温で加熱する処理であってもよい。この場合は、第２加熱装置２２での加熱温度である第２温度Ｔ２より高温で加熱することが好ましい。
以上では、紫外線照射処理は、大気ガス雰囲気下で行われるものとしたが、紫外線照射処理時に処理空間にオゾンガス等の酸化ガスを供給するようにしてもよい。また、上述のように、紫外線は照射せずに高温で加熱する場合にも、酸化ガスを供給するようにしてもよい。酸化ガスを供給することにより、密度向上用有機物の除去処理を短時間で行うことができる。In the above explanation, the removal treatment of the density-enhancing organic substance was a treatment of heating while irradiating ultraviolet rays. Instead of ultraviolet rays, other energy rays such as electron beams may be irradiated. Moreover, the removal process of the density-enhancing organic substance may be a process of simply heating the wafer W at a high temperature without irradiating it with energy rays. In this case, it is preferable to heat at a higher temperature than the second temperature T2, which is the heating temperature in the second heating device 22.
In the above description, it is assumed that the ultraviolet irradiation treatment is performed in an atmospheric gas atmosphere, but an oxidizing gas such as ozone gas may be supplied to the treatment space during the ultraviolet irradiation treatment. Further, as described above, even when heating at high temperature without irradiating with ultraviolet rays, oxidizing gas may be supplied. By supplying the oxidizing gas, the removal treatment of density-enhancing organic substances can be performed in a short time.

このように、密度向上用有機物の除去処理として種々の方法が採用できるため、密度向上用有機物として用いる有機化合物の選択肢が広い。そのため、有機チタン錯体や、密度向上用有機物以外の添加物の選択肢が広がる。つまり、本実施形態によれば、マスク層形成用液の選択肢が広い。 As described above, since various methods can be adopted as the removal treatment for the density-enhancing organic substance, there is a wide range of options for organic compounds to be used as the density-enhancing organic substance. This expands the options for additives other than organic titanium complexes and density-enhancing organic substances. In other words, according to this embodiment, there are a wide range of choices for the mask layer forming liquid.

なお、密度向上用有機物の除去処理に用いる紫外線として、ピーク波長が１５０～２００ｎｍ以外の紫外線、例えば、ピーク波長が２２２ｎｍや２５４ｎｍの紫外線を用いてもよい。この場合、紫外線照射処理時の処理空間にオゾンガス等の酸化ガスが供給される。 Note that as the ultraviolet light used for the removal treatment of the density-enhancing organic substance, ultraviolet light having a peak wavelength other than 150 to 200 nm may be used, for example, ultraviolet light having a peak wavelength of 222 nm or 254 nm. In this case, an oxidizing gas such as ozone gas is supplied to the processing space during ultraviolet irradiation processing.

本実施形態における処理対象層である、アモルファスシリコン層等は、これ自体ハードマスクであり、実際のエッチング対象層は例えばアモルファスシリコン層等より下層のＯＮＯ膜である。有機成分含有金属酸化膜のパターンを除去せずに、ＯＮＯ膜等のエッチング対象層のエッチングを、有機成分含有金属酸化膜のパターンとアモルファスシリコンのパターンが積層された積層パターンをマスクとして行ってもよい。また、ＯＮＯ膜等のエッチング対象層上に直接、有機成分含有金属酸化膜を形成し、ＯＮＯ膜等のドライエッチングを有機成分含有金属酸化膜のパターンをマスクとして行ってもよい。 The amorphous silicon layer or the like which is the layer to be processed in this embodiment is itself a hard mask, and the actual layer to be etched is, for example, an ONO film below the amorphous silicon layer or the like. Even if the layer to be etched, such as the ONO film, is etched without removing the organic component-containing metal oxide film pattern, using a layered pattern in which the organic component-containing metal oxide film pattern and the amorphous silicon pattern are stacked as a mask. good. Alternatively, a metal oxide film containing an organic component may be formed directly on a layer to be etched such as an ONO film, and dry etching of the ONO film or the like may be performed using the pattern of the metal oxide film containing an organic component as a mask.

以上の例では、第１温度Ｔ１での加熱と、第２温度Ｔ２での加熱を異なる装置で行っていたが、同一の装置で行ってもよい。言い換えると、第１加熱装置２１と第２加熱装置２２とは一体化されていてもよい。 In the above example, heating at the first temperature T1 and heating at the second temperature T2 were performed using different devices, but they may be performed using the same device. In other words, the first heating device 21 and the second heating device 22 may be integrated.

以上の例では、有機成分含有金属酸化膜の骨格を成す金属酸化膜は、酸化チタン膜であるものとしたが、酸化ジルコニウムや、酸化アルミニウム、酸化スズ膜等であってもよい。 In the above example, the metal oxide film forming the skeleton of the organic component-containing metal oxide film is a titanium oxide film, but it may be a zirconium oxide film, an aluminum oxide film, a tin oxide film, or the like.

以上の例では、密度向上用有機物が除去された後の有機成分含有金属酸化膜のウェットエッチングに、希フッ酸やＳＰＭを用いていたが、他のエッチング液を用いてもよく、有機成分含有金属酸化膜の膜種に応じてエッチング液を変更してもよい。 In the above example, dilute hydrofluoric acid or SPM was used for wet etching of the organic component-containing metal oxide film after the density-improving organic matter was removed, but other etching solutions may be used. The etching solution may be changed depending on the type of metal oxide film.

今回開示された実施形態はすべての点で例示であって制限的なものではないと考えられるべきである。上記の実施形態は、添付の請求の範囲及びその主旨を逸脱することなく、様々な形態で省略、置換、変更されてもよい。 The embodiments disclosed this time should be considered to be illustrative in all respects and not restrictive. The embodiments described above may be omitted, replaced, or modified in various forms without departing from the scope and spirit of the appended claims.

１３ 液膜形成装置
２１ 第１加熱装置
２２ 第２加熱装置
３１ 第１ドライエッチング装置
３２ 第２ドライエッチング装置
４１ 除去装置
４２ ウェットエッチング装置
Ｆ２ 液膜
Ｆ３ 有機成分含有酸化チタン膜
Ａ 添加物
Ｃ 有機チタン錯体
Ｋ ウェハ処理システム
Ｗ ウェハ
Ｙ 密度向上用有機物13 Liquid film forming device 21 First heating device 22 Second heating device 31 First dry etching device 32 Second dry etching device 41 Removal device 42 Wet etching device F2 Liquid film F3 Organic component-containing titanium oxide film A Additive C Organic titanium Complex K Wafer processing system W Wafer Y Organic substance for density improvement

Claims (7)

基板を処理する基板処理方法であって、
有機金属錯体、溶媒及び添加物を含む塗布液を基板に塗布し、前記塗布液の液膜を形成する工程と、
前記塗布液の液膜が形成された基板を加熱し、前記添加物に含まれる有機成分を含有する金属酸化膜である有機成分含有金属酸化膜を形成する工程と、
前記有機成分含有金属酸化膜をマスクとしてドライエッチングを行う工程と、
前記ドライエッチング後、前記有機成分含有金属酸化膜中の前記有機成分を除去する工程と、
前記有機成分含有金属酸化膜から前記有機成分を除去した膜をウェットエッチングにより除去する工程と、を有する、基板処理方法。 A substrate processing method for processing a substrate, the method comprising:
a step of applying a coating liquid containing an organometallic complex, a solvent, and an additive to a substrate to form a liquid film of the coating liquid;
heating the substrate on which the liquid film of the coating liquid is formed to form an organic component-containing metal oxide film that is a metal oxide film containing the organic component contained in the additive;
performing dry etching using the organic component-containing metal oxide film as a mask;
After the dry etching, removing the organic component in the organic component-containing metal oxide film;
A substrate processing method, comprising the step of removing a film from which the organic component has been removed from the organic component-containing metal oxide film by wet etching. 前記有機成分は、前記有機成分含有金属酸化膜の膜密度を向上させるためのものである、請求項１に記載の基板処理方法。 2. The substrate processing method according to claim 1, wherein the organic component is for improving the film density of the organic component-containing metal oxide film. 前記有機成分を除去する工程は、前記有機成分含有金属酸化膜が形成された基板を加熱しながら当該基板に紫外線を照射して、前記有機成分を除去する、請求項１または２に記載の基板処理方法。 3. The substrate according to claim 1 , wherein in the step of removing the organic component, the organic component is removed by irradiating the substrate with ultraviolet rays while heating the substrate on which the organic component-containing metal oxide film is formed. Processing method. 前記有機成分含有金属酸化膜を形成する工程は、前記有機金属錯体を加水分解させ且つ加水分解した前記有機金属錯体同士を脱水縮合させ、前記有機成分含有金属酸化膜を形成する、請求項１～３のいずれか１項に記載の基板処理方法。 The step of forming the organic component-containing metal oxide film comprises hydrolyzing the organometallic complex and dehydrating and condensing the hydrolyzed organometallic complexes to form the organic component-containing metal oxide film . 3. The substrate processing method according to any one of 3 . 前記有機成分含有金属酸化膜を形成する工程は、
前記塗布液の液膜が形成された基板を第１温度で加熱し、前記塗布液の液膜内の溶媒を除去する工程と、
前記塗布液の液膜から前記溶媒が除去された基板を前記第１温度より高い第２温度で加熱し、前記有機金属錯体を加水分解させ且つ加水分解した前記有機金属錯体同士を脱水縮合させ、前記有機成分含有金属酸化膜を形成する工程と、を有する、請求項４に記載の基板処理方法。 The step of forming the organic component-containing metal oxide film includes:
heating the substrate on which the liquid film of the coating liquid is formed at a first temperature to remove the solvent in the liquid film of the coating liquid;
heating the substrate from which the solvent has been removed from the liquid film of the coating liquid at a second temperature higher than the first temperature to hydrolyze the organometallic complex and dehydrate and condense the hydrolyzed organometallic complexes; 5. The substrate processing method according to claim 4, comprising the step of forming the organic component-containing metal oxide film. 前記有機成分含有金属酸化膜上にレジストパターンを形成する工程と、
前記レジストパターンを前記有機成分含有金属酸化膜に転写する工程と、をさらに有し、
前記ドライエッチングを行う工程は、前記レジストパターンが転写された前記有機成分含有金属酸化膜をマスクとして前記ドライエッチングを行う、請求項１～５のいずれか１項に記載の基板処理方法。 forming a resist pattern on the organic component-containing metal oxide film;
further comprising the step of transferring the resist pattern to the organic component-containing metal oxide film,
6. The substrate processing method according to claim 1, wherein in the step of performing dry etching, the dry etching is performed using the organic component-containing metal oxide film to which the resist pattern has been transferred as a mask. 基板を処理する基板処理システムであって、
有機金属錯体、溶媒及び添加物を含む塗布液を基板に塗布し、前記塗布液の液膜を形成する液膜形成装置と
前記塗布液の液膜が形成された基板を加熱し、前記添加物に含まれる有機成分を含有する金属酸化膜である有機成分含有金属酸化膜を形成する加熱装置と、
前記有機成分含有金属酸化膜をマスクとしてドライエッチングを行うドライエッチング装置と、
前記ドライエッチング後、前記有機成分含有金属酸化膜中の前記有機成分を除去する除去装置と、
前記有機成分含有金属酸化膜から前記有機成分を除去した膜をウェットエッチングにより除去するウェットエッチング装置と、を有する、基板処理システム。 A substrate processing system that processes a substrate,
A liquid film forming apparatus that applies a coating liquid containing an organometallic complex, a solvent, and an additive to a substrate and forms a liquid film of the coating liquid; and a liquid film forming apparatus that heats the substrate on which the liquid film of the coating liquid is formed; a heating device for forming an organic component-containing metal oxide film, which is a metal oxide film containing an organic component contained in the organic component;
a dry etching device that performs dry etching using the organic component-containing metal oxide film as a mask;
a removal device that removes the organic component in the organic component-containing metal oxide film after the dry etching;
A substrate processing system comprising: a wet etching apparatus that removes a film from which the organic component has been removed from the organic component-containing metal oxide film by wet etching.
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